The Chemistry of Hydrochalcogenides

研究了三tyene -9-硒酸（TripSeSeH， Trip为9-三甲酰基）的合成。二硒化合物TripSeSeC(O)R.1.1的合成。硒-9-三丁基三丁烯-9-硒代硒酸盐[TripSe(O)SeTrip]与硒羧酸[RC(O)SeH]反应得到所需的TripSeSeC(O)R，产率高。对苯基和苯基被用作取代基R.1.2。硒醇tripsh用碱处理，得到的TripSe^-与元素硒反应，然后用碘化甲酯淬灭混合物，得到相应的二硒化物TripSeSeMe。这一结果表明TripSeSe的形成。当混合物用酸淬火时，TripSeH被回收。使用单质硫而不是硒，以15%的产率生成了TripSeSH。用苯甲酰氯和乙酰氯分别淬火制备了二硒化物、TripSeSe(O)-p-Tol和TripSeSeC(O)Me。水解TripSeSeC(O) r在酸性或碱性条件下水解TripSeSeC(O)-p-Tol，得到硒醇（TripSeH）和三硒烯（TripSeSeSeTrip）为主要产物。在二氯甲烷和乙醇的混合溶剂中，用高氯酸在40℃下水解TripSeSeC(O)Me，得到TripSeSeC和TripSeSeSeTrip的类似混合物，比例为1:1。TripSeSeSeTrip是由中间体生成的TripSeSeH二聚化形成的，并伴随着H_2Se的消除。TripSeH的形成表明了TripSeH的脱盐作用。

The synthesis of triptycene-9-selenoselenenic acid (TripSeSeH;Trip denotes 9-triptycyl hereafter) was investigated.1.Synthesis of diselenides, TripSeSeC(O)R.1.1.The reaction of Se-9-triptycyl triptycene-9-selenoseleninate [TripSe(O)SeTrip] with selenocarboxylic acids [RC(O)SeH] yielded the desired TripSeSeC(O)R in high yields. p-Tolyl and benzyl groups were employed as the substituent R.1.2.Selenol, TripSeH, was treated with a base, and the resulting TripSe^-was allowed to react with elemental selenium, followed by quenching the mixture with methyl iodide to give the corresponding diselenide (TripSeSeMe). This result indicated the formation of TripSeSe. When the mixture was quenched with acid, TripSeH was recovered. Using elemental sulfur, instead of selenium, led to the formation of TripSeSH in 15% yield. Diselenides, TripSeSe(O)-p-Tol and TripSeSeC(O)Me were prepared by quenching the mixture with benzoyl chloride and acetyl chloride, respectively.2.Hydrolysis of TripSeSeC(O)RHydrolysis of TripSeSeC(O)-p-Tol was carried out under acidic or basic conditions to give the selenol (TripSeH) and the triselenide (TripSeSeSeTrip) as the main products. Hydrolysis of TripSeSeC(O)Me with perchloric acid in a mixed solvent of dichloromethane and ethanol at 40℃ gave a similar mixture of TripSeH and TripSeSeSeTrip in a ration of 1:1. TripSeSeSeTrip would be formed by a dimerization of intermediary generated TripSeSeH accompanying with elimination of H_2Se. The formation of TripSeH suggests the deselenation of TripSeSeH.